Reactive polymeric dyes

ABSTRACT

Reactive polymeric dyes are provided comprising a chromophoric moiety derived from at least one free radically polymerizable dye and an azlactone moiety derived from 2-alkenylazlactone such that the free radically polymerizable dye is incorporated into the backbone of the polymer. Alternatively, 2-alkenylazlactone is polymerized and then derivatized with a nucleophilic dye or dyes, such that the chromophoric portion of the dye is pendent to the polymer backbone. Both types of reactive polymeric dyes may also contain additional polymerized monomeric units. The reactive polymeric dyes of the present invention can be used in a photoresist system and in particular in a color proofing construction.

This is a division of application No. 08/052,337, filed Apr. 23, 1993,now U.S. Pat. No. 5,362,812.

TECHNICAL FIELD

This invention relates to polymeric dyes, the preparation and usethereof, and more particularly to reactive polymeric dyes useful inphotoresist constructions and more particularly in aqueous developablecolor proofing constructions, as well as other color imagingconstructions.

BACKGROUND OF THE INVENTION

In the graphics arts, it is often desirable to produce a four or morecolor proof from image data to assist a printer in correcting a set ofcolor prints prior to using the image data to produce color plates andalso to reproduce the color quality that will be obtained during theprinting process. The proof must be a consistent duplication of the halftone image from a printing process, and should neither gain nor losecolor in comparison to the printed image. Visual examination of a colorproof should show the following characteristics:

1. defects on the negatives,

2. best color rendition to be expected from press printing of thematerial,

3. correct gradation of all colors and whether grays are neutral, and

4. need, if any, for subduing one of the colors and/or giving directionsfor altering the film negatives before making the printing plates.

Color proofing for multi-colored printing without the use of pre-presscolor proofs are made by using a printing press or a proof press takingall the steps necessary for actual multicolor printing. Such aconventional method of color proofing is costly and time consuming.

Photographic processes are known that use photopolymers. There arevarious types of photographic color proofing methods, for example, thesurprint type (laminated single sheet) and the overlay type.

Presently, aqueous developable color proofing constructions utilizeresin-dispersed pigments. Such resins have to provide a good pigmentdispersion but must also be compatible with photooligomers orphotopolymers used in the color proofing construction. Unfortunately,dispersed pigments are prone to migration into adjacent layers of theproofing construction, thus contributing to colorant bleeding.

In the overlay type of color proofing method, an independent transparentplastic support is used for producing a print of each color separationfilm by applying a photosensitive layer of the corresponding color. Aplurality of such supports carrying prints of corresponding colors arethen superimposed upon each other on a white sheet to produce a colorproof. The primary advantage of overlay type of color proofing is thatit is quick and can serve as an overlay proof by combining at leastthree or four colors in register.

In the surprint (adhesively laminated single sheet construction) type ofcolor proofing method, a color proof is prepared by successivelyproducing prints of different colors from different color separationfilms, respectively, by applying a photosensitive coating ofphotopolymers of corresponding color on the opaque support insuccession. Alternatively, each color separation can be prepared byapplying a photosensitive coating of photopolymers of the correspondingcolor to a strippable support base film and then adhesively laminatingthe separate color prints together, in register, to prepare a full colorproof. Some examples are described in U.S. Pat. Nos. 3,671,236 and3,136,637. An advantage of this surprint type of color proof is that thecolor saturation is not influenced by the plastic support. This methodmore closely resembles the actual printing process and eliminates thecolor distortion inherent in the overlay system.

An another example of a color-proofing system is one described in U.S.Pat. No. 3,671,236 wherein a light-sensitive continuous color layer isreleasably attached to a carrier. Overlaying the color layer is awater-insoluble transparent colorless barrier layer, to the oppositesurface of which can be applied a pressure-sensitive adhesive. Uponlamination of the sheet to a substrate, and removal of the carrier, thecolor layer is formed onto an image, photomechanically, by removalthereof in the non-image areas.

In addition to overlay or surprint types of color proofing, otherprocesses for producing copies of an image embodying aphotopolymerization and thermal transfer techniques are known. Someexamples are described in U.S. Pat. Nos. 3,060,023, 3,060,024,3,060,025, 3,481,736, and 3,607,264. Generally, in these processes, aphotopolymerizable layer coated on a suitable support is exposed,imagewise to a process transparency. The surface of the exposed layer isthen pressed into contact with the image receptive surface of a separateelement and at least one of the elements is heated to a temperatureabove the transfer temperature of the unexposed portions of the layer.The two elements are then separated, whereby the thermally transferable,unexposed image areas of the composition transfer to the image receptiveelement. If the element is not precolored, the tacky unexposed image maynow be selectively colored with a desired toner. The colored matteradheres, preferentially, to the clear unpolymerized material. Sincelamination, exposure and development are carried out for the respectivecolors, in sequence, these processes are generally time consuming.

Typically, the proofing constructions add an oxygen barrier between thesupport base film and the colorant layer. However, such barriers canfracture along the edges of the transparent sheet, or along the peelfront, thus permitting entry of oxygen. The oxygen prohibitsphotopolymerization. Furthermore, several barriers are susceptible towater damage and render the construction ineffective and non-functional.

U.S. Pat. No. 4,239,868 teaches the preparation and use of structurallycolored cross-linkable compositions. These materials are formed by thecopolymerization of free-radically polymerizable dyes and acrylates withpendent hydroxy functionality. The hydroxyl groups are subsequentlyderivatized with an ethylene-containing group, to render the coloredpolymer cross-linkable. The polymers have relatively low molecularweights, that is, in the range of 1,000-12,800 Daltons.

Examples of other polymeric dyes developed had molecular weight in therange of 4500-5000 and can contained up to 15% dye. For example, anionomeric macromolecular dye based on polyvinylamine and used infoodstuffs are described in U.S. Pat. Nos. 3,920,855, 3,937,851,4,275,002 and 4,279,662.

SUMMARY OF THE INVENTION

Briefly, in one aspect of the present invention reactive macromoleculardyes (also referred to as reactive polymeric dyes) are providedcomprising a chromophoric moiety derived from at least one freeradically polymerizable dye and an azlactone moiety derived from2-alkenylazlactone such that the free radically polymerizable dye isincorporated into the backbone of the polymer. Alternatively,2-alkenylazlactone is polymerized and then derivatized with anucleophilic dye or dyes, such that the chromophoric portion of the dyeis pendent to the polymer backbone. Both types of reactive polymericdyes may also contain additional polymerized monomeric units.

Advantageously, these reactive polymeric dyes may contain otherfunctional moieties derived by incorporating various nucleophiles intothe polymer. As used in this application "reactive" means the propertiesof the polymeric dye may be modified or altered by a nucleophilicreaction to provide additional functionality, such as solubilization,cross-linking, or compatibility. Alternatively, the polymeric dye may bemodified by using other polymerizable monomeric units. The reactivepolymeric dyes have a number average molecular weight of 5,000 to5,000,000 Daltons. These reactive polymeric dyes are excellent materialsfor use in an aqueous developable color proofing construction, as wellas being particularly useful in a dry peel apart construction. Thereactive polymeric dyes display excellent shelf stability and oxygeninsensitivity.

The advantages of the reactive polymeric dyes of the present inventionin photoresist systems and in particular in aqueous developable colorproofing systems include (1) no need to disperse pigments in resinbinder systems, (2) no diffusion of pigment into accompanying layers ofthe construction, (3) molecular high transparency, (4) excellent shelfstability, (5) polymeric mechanical properties, and (6) improvedhandling features.

In another aspect of the present invention, a proofing film constructionis provided comprising:

(a) a flexible support base film; and

(b) a colorant layer comprising a reactive polymeric dye and adjuvants.

In yet another aspect of the present invention, a transparent adhesivelayer may be added to the construction, with a barrier layer between thecolorant layer and the adhesive layer.

As used in this application:

"absorptivity coefficient" can be used interchangeably with extinctioncoefficient;

"ancillary ligand" refers to an essentially colorless organic group,which is bound to the metal center by the donation of a lone pair ofelectrons or in the case of multidentate groups by the donation of twoor more pairs of electrons in order to satisfy the coordinationrequirement; these groups are considered auxochromic groups formetal-containing dyes; ancillary ligands can be neutral or negativelycharged, further ancillary ligands can be monodentate or polydentate(e.g. bidentate) and may include: water, ammonia, halide (-1 ) (e.g.fluoride (-1 ), chloride (-1), etc.), thiocyanide (-1), cyanide (-1),azide (-1), carbon monoxide, alkyl or aryl isocyanides, alkyl and arylnitriles (e.g. acetonitrile, benzonitrile), alkyl and aryl phosphines(e.g. trimethylphosphine, triphenylphosphine, diethylphenylphosphine,alkyl and aryl amines, diamines (e.g., ethylenediamine,1,2-benzenediamine), polyamines, alkylsulfides, arylsulfides,heteroarenes (e.g., pyridine, imidazole, quinoline, 2,2'-bipyridine,1,10-phenanthrolene, etc.), nitrate (- 1 ), sulfate (-2), oxalate (-2),alkyldiketonates (-1) (e.g., acetylacetonate (-1)), 8-hydroxyquinolate(-1);

"dye" refers to any molecule absorbing electromagnetic radiation between350 nm and 1200 nm, such that the molar absorptivity coefficient of thematerial exceeds 1000 liters/mole-cm somewhere in the aforementionedregion;

"dye nucleus" refers to the principle chromophore in a dye molecule;

"dye moiety" refers to an organic radical derived from abstracting anatom such as hydrogen or chlorine from either the dye nucleus or anauxochromic group;

"auxochromic group" refers to a group that when attached to achromophoric moiety substantially shifts the principal wavelength ofabsorption in the dye molecule;

"auxochromic moiety" refers to an organic radical derived fromabstracting an atom from an auxochromic group;

"chromophore" refers to the portion of a dye molecule that issubstantially responsible for the absorption of electromagneticradiation in the dye molecule; dyes are sometimes classified on thebasis of their principle chromophore; for metallized dyes (i.e.,metal-azo dyes, metal-azomethine dyes, metal formazan dyes, orphthalocyanine dyes), the term "chromophore" refers to theorganic-derived ligand containing the principle light absorbingcomponent (e.g., 2,2'-azobis[phenolato](-2),[1-[(2-hyroxyphenyl)azo]-2-naphthalenolato](-2), the double deprotonateddianion of[2-[N-(2-hydroxy-3,5-dinitrophenyl)formimidoyl]-3,5-dimethoxy]phenol,deprotonated phthalocyanine dianion) and the metal;

"chromophoric moiety" refers to a radical generated by abstracting anatom from a dye nucleus; and

"metal-containing dye fragment" refers to a metallized dye chromophore,as defined above, which may also possess one or more ancillary ligands,with the proviso that at least one vacant, available coordination sitealso be present on the metal.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Macromolecular colorants are an alternative class of coloring material,possessing many of the best properties of the conventional colorants.Polymeric colorants were extensively developed in the early 1970's,however, this versatile class of colorants has not been extensively usedfor imaging applications. For the most part, the polymeric colorantsthat have been used in imaging applications have been simple copolymersand the principle advantage of these materials has been to reduce themobility of the colorant. The availability of new functionalizablecomonomers has allowed for the development of more versatilemacromolecular colorants which can be used in imaging media.

The reactive polymeric dyes of the present invention can be used in aphotoresist system and in particular in a color proofing construction.Photoresists are essentially systems where a layer of material that issensitive to light is coated onto a surface and then exposed to actinicradiation generally in the visible and near UV regions of theelectromagnetic spectrum through a master-image, mask or pattern. Thiscauses a change of some of the properties of the layer such assolubility, softening point or Tg, etc. This change in the layermaterial properties allows for parts of the layer to be removed leavingan imagewise stencil on the support.

Some examples of photoresist systems include: (1) crosslinking of alight sensitive colloid or synthetic polymer by the addition of aphotosensitizer that causes decomposition to form an active species thatinsolubilizes the surrounding binder, for example dichromate/gelatin orazide/rubber; (2) polymers containing photosensitive groups built insitu of the structures, forming crosslinks between their molecules onexposure to actinic radiation, to significantly lower their solubilityor softening point; and (3) photopolymerization providing a means ofinsolubilization or increase of softening point, whereby monomericcompounds are made to polymerize via actinic radiation with or without aphotosensitizer/initiator present.

A primary application of such a color proofing construction is anaqueous developable color proofing system. This color proofingconstruction can be used in an overlay construction, a single sheetconstruction, or for thermal transferographics, as well as in dry peelapart constructions.

The color proofing construction of the present invention comprises aflexible support base film, and coated thereon, a colorant layercomprising the reactive polymeric dyes of the present invention, whereinthe colorant layer is an aqueous developable imaging layer or thermallytransferable layer.

Contemplated to be within scope of the present invention are variouscolor proofing construction configurations. Amongst the variousconfigurations are the following non-limiting examples:

(1) in sequential order, (a) a flexible support base film, and (b) acolorant layer;

(2) in sequential order, (a) a flexible support base film, (b) acolorant layer coated thereon, and (c) an oxygen barrier layer coated onthe surface of the colorant layer;

(3) in sequential order, (a) a flexible support base film, (b) acolorant layer, and (c) an adhesive layer;

(4) in sequential order, (a) a flexible support base film, (b) an oxygenbarrier layer, and (c) a colorant layer, wherein the base film has arelease surface;

(5) in sequential order, (a) a flexible support base film, (b) acolorant layer coated thereon, (c) a barrier layer, and (d) an adhesivelayer, wherein the barrier layer protects the colorant layer from theadhesive layer and vice versa;

(6) in sequential order, (a) a flexible support base film, (b) an oxygenbarrier, (c) an colorant layer, and (d) an adhesive layer; and

(7) in sequential order, (a) a flexible support base film, (b) an oxygenbarrier layer, (c) a colorant layer, (d) a barrier layer to protect thecolorant layer from an adhesive layer and (e) the adhesive layer,wherein the base film has a release surface.

The reactive polymeric dyes of the present invention comprise a dyemoiety derived from at least one free radically polymerizable dye and anazlactone moiety derived from 2-alkenylazlactone such that the freeradically polymerizable dye is incorporated into the backbone of thepolymer. Alternatively, 2-alkenylazlactone is polymerized and thenderivatized with a nucleophilic dye or dyes, such that the chromophoricportion of the dye is pendent to the polymer backbone. Both types ofreactive polymeric dyes may also contain additional polymerizedmonomeric units. Furthermore, these reactive polymeric dyes may containother functional moieties derived by incorporating various nucleophilesinto the polymer. The reactive polymeric dyes may be prepared accordingto the following flow chart, following either Path 1 or Path 2: ##STR1##

Although the flow chart indicates the reactive polymeric dyes can eitherbe a copolymer (A1) or a derivatized azlactone homopolymer (B2) it iswithin the scope of the present invention to include optional additionalmonomers in the polymerizable compositions. For example, following Path2, the 2-alkenylazlactone derivatized polymer (the polymer produced atA2), need only have as little as 1 mole % of a2-alkenylazlactone-derived monomeric unit. Any art known monomers may beadded to the polymerizable compositions (A1 and A2 precursorcompositions), provided the monomers do not nucleophilically react withthe 2-alkenylazlactone. Preferably, the A2 polymer is a homopolymer.Likewise, the A1 polymer need only contain as little as 1 mole % of2-alkenylazlactone. For the reactive polymeric dyes of either A1 or B2type, the polymerizable dye or nucleophilic dye is typically present inthe range of 0.5 to 99 mole % of 2-alkenylazlactone.

Advantageously, the reactive polymeric dye of type A1, described byFormula I, are color stable polymeric dyes and could be blended withother art known polymers, as well as being color stable intermediates.##STR2## wherein "Az" represents monomeric azlactone residue and "Dye"represents the free radically polymerizable dye residue. Preferably, thepolymers are derivatized to incorporated various nucleophiles into thereactive polymeric dye, such as described in Formula II.

Once the reactive dye polymers (A1 and B2) have been prepared, thepolymers may be further functionalized with other functional moietiesderived by incorporating various nucleophiles into the polymer. While itis preferable that all the azlactone moieties are functionalized, it iswithin the scope of the present invention that as much as 99.9% of theazlactone moieties could remain unreacted. Although, it is possible tofunctionalize 100% the azlactone moieties, such a polymeric dye is notreactive within the scope of the present invention but is useful incombination with the reactive polymeric dyes of the present invention. Anon-limiting list of various nucleophiles contemplated are illustratedand discussed below.

The reactive polymeric dyes may be prepared using 2-alkenylazlactone asa polymerizable monomer. 2-Alkenylazlactones are well-known and theirsynthesis, physical and chemical properties, homo- and copolymerizationbehavior, and preparations and applications are discussed in a recentreview by Rasmussen et al. Encyclopedia of Polymer Science andEngineering, "Polyazlactones," 2nd ed.; 1988; Vol. 11, pp 558-571.Useful 2-alkenylazlactones for the present invention include2-vinyl-4,4-dimethyl-2-oxazolin-5-one,2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one,2-vinyl-4-ethyl-4-methyl-2-oxazolin-5-one,2-vinyl-4,4-diethyl-2-oxazolin-5-one,2-vinyl-4-methyl-4-phenyl-2-oxazolin-5-one,2-isopropenyl-4,4-tetramethylene-2-oxazolin-5-one,2-vinyl-4,4-pentamethylene-2-oxazolin-5-one, and2-vinyl-4,4-dimethyl-2-oxazolin-6-one. The preferred 2-alkenylazlactonemonomer is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

Polymerization of the azlactone monomers with themselves or togetherwith free radically polymerizable dyes may be accomplished eitherthermally (for example, through the decomposition of acyl peroxides,dialkyl percarbonates, azoalkanes, etc.) or azo compounds, such as2,2'-azobis(2-methylpropionitrile) or photochemically (such asphotolysis of bisimidazoles, benzoin ethers, aromatic ketones, orhalomethyl-s-triazines) means well known in the art.

The polymerized 2-alkenylazlactone can then be nucleophilicallysubstituted to provide polymeric dyes with further functionality, whichmay impart reactivity. The azlactone residual component can be easilyfunctionalized with a variety of nucleophiles using either acid or basecatalysts. The number average molecular weight of the resulting polymer,as determined by light scattering techniques, is in the range of 5,000to 5,000,000 Daltons.

Dye monomers useful to form the A1 polymers should contain oneethylenically unsaturated, polymerizable group, selected from vinyl,acryl, methacryl, acrylamide, methacrylamide, or allyl. Generally,useful dyes monomers are any molecules absorbing electromagneticradiation between 350 nm and 1200 nm such that the molar absorptivitycoefficient, also referred to as the extinction coefficient, of thematerial exceeds 1000 liters/mole-cm somewhere in the aforementionedregion. Typically, dyes are classified according to the chromophoricmoiety of the dye. Nonlimiting examples of such principle moieties areanthraquinone, azo, azomethine, aminostyryl, phthalocyanine,indoaniline, formazan, metal-azo, metal-azomethine and metal-formazan.For metallized dyes, the principle moiety refers to both the metalcenter and the organic chromophore-containing ligand. Other essentiallycolorless organic groups ligated to the metal center of a metallized dyeare referred to as "ancillary ligands." Other useful principle moietiescan be selected from the classes described in D. W. Bannister, A. D.Olin, H. A. Stinge, "Dyes and Dye Intermediates," Kirk-OthmerEncyclopedia of Chemical Technology, 3rd ed., 159-212 (1979).

The dye monomers may also contain an auxochromic group, which whenattached to the chromophore substantially shifts the principalwavelength of absorption in the dye molecule. Typically auxochromicgroups include, NH₂, NHR, NR₂, OH, OR, SH, SR, NHCOR, NHSO₂ R, where Ris any alkyl or aryl group. When the dye is a metal-containing dye, theauxochromic group can also include ancillary ligands. These organicgroups are generally referred to as ligands and include, for examplepyridine, water, ammonia, and amines. Other examples of ligands aredescribed in F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry,4th ed., John Wiley & Sons, New York, 107-194 (1980). Preferredauxochromic groups for metallized dyes are nitrogen-containingheterocyclic, for example, pyridine and imidazole.

Where the term "group" is used in describing substituents, substitutionis anticipated that does not interfere with the function of the compoundbeing substituted. For example, the term "alkyl group" includes ethergroups (e.g., CH₃ CH₂ CH₂ OCH₂), haloalkyls, nitroalkyls, carboxyalkyls,hydroxyalkyls, sulfoalkyls, etc. wherein the "term" alkyl includeshydrocarbons of 1 to 20 carbon atoms. Substituents that react withactive ingredients, such as strong reducing or oxidizing substituents,are excluded as not being sensitometrically inert or harmless.

A preferred class of dye monomers can be prepared from dyes containinghydroxy or amino groups, for example those prepared by the reaction ofacryloylchloride or alkacryloylchloride shown in the following equation:##STR3## wherein A is a dye moiety derived from the following dyeclasses: anthraquinone, azo, aminostryl, phthalocyanine, indoaniline; Xis either an oxygen atom or a nitrogen atom; and R is either a hydrogenatom or an alkyl group having 1-18 carbon atoms. Representative examplesof A-XH include 1-aminoanthraquinone, Disperse Red1,1-(3-hydroxypropylamino) anthraquinone. Nonlimiting examples ofacryloyl and methacryloyl containing dyes are described U.S. Pat. No.4,614,521, section [D], "Sublimable dyes having an acryloyl or amethacryloyl group" and such description is incorporated herein byreference.

Another class of useful polymerizable dyes are metal-azo ormetal-azomethine dyes in which a polymerizable heterocycle such as4-vinylpyridine, 1-vinylimidazole are ligated to a metal center. Suchdyes are described in U.S. Pat. No. 5,166,326 and such description isincorporated herein by reference.

Yet another class of polymerizable dyes are those containing a styrylmoiety. These materials may be prepared, for example, by thenucleophilic aromatic substitution of a halogen-containing precursors by4-aminostyrene. Particularly useful halogen-containing precursors fromthe anthraquinone class include, for example, 1-chloroanthraquinone,1-amino-2-methyl-4-bromoanthraquinone. Examples of polymerizablemonomeric anthraquinone dyes may be found in R. S. Asquith, H. S. Blair,A. A. Crangle, E. Riordan "Self-Colored Polymers Based onAnthraquinones" Journal of the Society of Dyers and Colorists, Apr.,1977, pp 114-125.

Useful monofunctional nucleophilic dyes are dyes with a nucleophilicreactive group selected from amino, hydroxy, hydroxyalkyl, mercaptoalkylor aminoalkyl groups. Particularly useful dyes are those where thenucleophilic reactive group is either a hydroxy group or an amino groupthat is pendent to a dye nucleus and not directly bound to the dyenucleus. When the nucleophilic reactive group is an amino group, it ispreferred the amine be a primary amine. Preferably the nucleophilicreactive group is attached to the dye nucleus via an auxochromic groupthrough a linking group. The preferred linking groups are small alkylchains, for example, methylene, ethylene, or propylene. Nonlimitingexamples of useful nucleophilic dyes are described in U.S. Pat. No.4,614,521, section [A], "Sublimable dyes capable of reacting with anepoxy group or isocyanate group" and such description is incorporatedherein by reference.

Advantageously, the resulting polymer can be crosslinkable, non-tackyand easily processed, whereas certain commercial photooligomers aretacky and create processing difficulties. Another advantage is therelative oxygen insensitivity of the reactive polymeric dyes. Althoughthe use of an oxygen barrier coat is not outside the scope of thepresent invention.

The reactive polymeric dyes are soluble in a variety of solventsincluding non-chlorinated solvents, such as MEK and water-basedsolvents, such as water, and water miscible organic solvents. Thisallows coating of a polymer-containing formulation for a color proofingconstruction from a more environmentally acceptable solvent. Thepolymers are compatible with a wide range of polymers useful in thegraphic arts. Another advantage of using the polymer of the presentinvention is improved shelf stability over certain commerciallyavailable photooligomers. One of the advantages of the reactivepolymeric dyes of the present invention is that the dyes take on thecharacteristics of the polymer, that is, the reactive polymeric dyesavoid the problems associated with low molecular weight polymeric dyesor monomeric dyes.

The reactive polymeric dyes of the present invention, which may be blockor random, preferably random, and which have homo- or copolymericbackbones, are illustrated in the following block diagram: ##STR4##

The reactive polymeric dyes of the present invention can beschematically described by combining the various blocks as identifiedabove. The relative amounts of the monomeric units are not described atthis point other than to point out, that in each configuration, thepolymer contains at least one of C or D units with the proviso that whenD units are present (that is, no C units are present) then at least oneof A, B or a unit containing an azlactone derived moiety (E unit) isalso present. For example, a useful reactive polymeric dye of thepresent invention would comprise A+C or D units, optionally including Band E units. Such alternative variations would include, ABC, ABD, ABCD,and ABCDE. Preferably, the reactive polymeric dyes comprise ahomopolymeric backbone ABC or the copolymer ABD and optionally E units,and more preferably the polymers comprise the copolymer of ABD units.

The above block diagram can be represented by the following formula:##STR5## wherein R can be hydrogen or an alkyl group containing 1 to 18carbon atoms;

R¹ can be: ##STR6## n is 0 or 1; R⁷, R⁸, R⁹, and R¹⁰ can beindependently an alkyl group having 1 to 12 carbon atoms or a cycloalkylgroup having 5 to 12 carbon atoms, an aryl or aralkyl group having 6 to12 carbon atoms or at least one of the pairs R⁷ and R⁸, or R⁹ and R¹⁰,taken together with the carbon to which it is joined forms a 5- or6-membered carbocyclic ring, or any of R⁷, R⁸, R⁹ and R¹⁰ may be H whenn is 1; preferably R⁷ and R⁸ are methyl and n is 0;

W can be --NR¹⁴ --, --S-- or --O--, wherein R¹⁴ can be a hydrogen, arylor alkyl of 1 to 12 carbon atoms; preferably W can be --O-- or --NH--;

R² can be a polymerizable, ethylenically unsaturated group selected from(a) --R¹¹ --W--T in which R¹¹ can be an alkylene group having 1 to 12carbon atoms, an arylene group having 6 to 10 carbon atoms, anoxyalkylene group or a poly(oxyalkylene) in which the alkylene group has2 to 6 carbon atoms and the number of oxygen atoms is a positive integerless than or equal to four, most preferably R¹¹ has from 1 to 4 carbonatoms; W is as previously defined, and T is an ethylenically unsaturatedgroup selected from the group consisting of acryloyl, methacryloyl,cinnamoyl, maleoyl, fumaroyl, itaconoyl, and crotonoyl, and ispreferably acryloyl or methacryloyl; ##STR7## in which R¹¹ is as definedas in (a); R¹² and R¹³ independently can be hydrogen, cyano, a carboxylgroup, a --C(═O)NH₂ group, an alkyl group having 1 to 12 carbon atoms,or a phenyl group or naphthyl group optionally having substitutionthereon which can be, for example, halogen, an alkyl or alkoxy groupfrom 1 to 4 carbon atoms;

R³ can be: ##STR8## n is 0 or 1; R⁷, R⁸, R⁹ and R¹⁰ are as describedabove and

Z can be a carboxyl, or aminocarbonyl, where the carboxy group has theformula COOW¹, and the aminocarbonyl group has the formula CONR¹⁴ W¹ ;

W¹ can be a solubilizing cation (e.g., sodium, potassium, or quaternaryammonium) ionically bonded to a negatively charged atom such as O⁻ orS⁻, a hydrogen atom or (Q¹)_(x) --(A)_(y) wherein Q¹ is a linking group,x is 1 or 2 and y is 1 to 10. Q¹ comprises polyvalent linking groupssuch as polyvalent aliphatic moieties, for example, --CH₂ --, --CH₂ CH₂-- and --CH₂ CH(CH₂)₂ ═, polyvalent aromatic moieties, for example,phenylene, polyvalent aralkyl moieties, or polyvalent alkaryl moieties,carbonyl, sulfonyl, either alone or in combination. Q¹ can be linear orbranched and can contain other polyvalent moieties, such as oxy, thio,--NHSO₂ --, --NHCO--, and --NH-- interspersed between polyvalentaromatic or polyvalent aliphatic groups. Combinations of linkingmoieties include oxyalkylene, iminoalkylene, or iminoarylene. Q¹ may bemultifunctional, that is, capable of bonding to more than one A group.Non-limiting examples of Q¹ include alkylene, arylene groups (e.g.,propane-1,3-diyl, ethane-1,1,2-triyl, methylene, dodecane-1,12-diyl,phenylene), oxa-substituted alkylene groups (e.g., 2-oxapropan-1,3-diyl,3-oxapentan-1,5-diyl), aza-substituted alkylene groups (e.g.,2-azapropan-1,3-diyl, 3-methyl-3-azapentan-1,5-diyl), and the like.Nonlimiting examples of A include carboxy group (--COOH), phospho group(--PO₃ H₂), and sulfo group (-- SO₃ H) and their salts with alkalimetals (e.g., sodium, lithium, potassium), mono-, di-, tri-, andtetra-substituted ammonium salts (e.g., ammonium, tetrabutyl ammonium,phenyldipropylammonium). Preferably, A is a carboxyl group, sulfo group,or phospho group or an alkali metal or tetra-substituted ammonium saltsthereof.

It is possible to incorporated the quaternary ammonium salt group intothe polymer by reaction with the formed polymer via a coupling reaction(such as coupling through an azlactone group with a nucleophilesubstituted quaternary ammonium salt), or by quaternization of atertiary amine bound to the polymer, it is also possible to copolymerizethe polymer with a quaternary ammonium salt-containing monomer. It isalso possible to incorporate a quaternary ammonium salt into the polymervia deprotonation of the carboxyl group (when W¹ is H) withtetrabutylammonium hydroxide or tetramethylammonium hydroxide.

R⁴ is (Q²)_(i) --(D)_(j) wherein Q² is a linking group and D is a dyemoiety or a metal-containing dye fragment, i is 1 or 2 and j is 1 to 10depending on the value of i and the multifunctional nature of Q². Theatom in Q², which is covalently bonded to W is typically a carbon atom,however the bonding atom may be a sulfur atom provided W is a nitrogenand the sulfur atom is part of a sulfinyl or sulfonyl group. Q² is apolyvalent linking group, such as polyvalent aliphatic groups, forexample, --CH₂ --, --CH₂ CH₂ -- and --CH₂ CH(CH₂)₂ ═, polyvalentaromatic groups, for example, phenylene, polyvalent aralkyl groups, orpolyvalent alkaryl groups, carbonyl, sulfonyl, either alone or incombination. Q² can be linear or branched and can contain otherpolyvalent moieties, such as oxy, thio, --NHSO₂ --, --NHCO--, and --NH--either interspersed between polyvalent aromatic or polyvalent aliphaticgroups or terminating in these groups. One particularly usefulembodiment is where Q² is a small (1-6 carbon atoms) alkylene grouporiginating on W and terminating, that is, attaching to D with, --NH--,--S--, SO₂ NH--, --CONH₂ --. Alternatively, Q² can comprise anauxochromic ligand moiety containing a nitrogen-containing heterocyclicmoiety, such as pyridyl. Q² can also comprise a linking group as definedfor Q¹, which terminates in an auxochromic ligand moiety, that is,pyridyl or imidazolyl. Q² may contain up to 50 atoms including carbon,nitrogen, sulfur, and non-peroxidic oxygen atoms. Combinations oflinking groups include oxyalkylene, iminoalkylene, iminoarylene. Q² canbe coordinated to a metal containing dye fragment or covalently bondedto a metallized dye moiety. In a particularly useful embodiment Q² is alower alkyl group having 1 to 6 carbon atoms and terminating with anauxochromic ligand derived from a nitrogen-containing heterocyclicmoiety, for example, 3--CH₂ Py (where Py is a pyridyl radical) when D isa metal-containing dye fragment. Nonlimiting examples of Q² includealkylene, arylene groups (e.g., propane-1,3-diyl, methylene,dodecane-1,12-diyl, phenylene), oxa-substituted alkylene groups (e.g.,2-oxapropan-1,3-diyl, 3-oxapentan-1,5-diyl), aza-substituted alkylenegroups (e.g., 2-azapropan-1,3-diyl, 3-methyl-3-azapentan-1,5-diyl), andthe like. Q² can be bonded to a chromophoric moiety either directly orthrough an auxochromic group. Nonlimiting examples of D are radicalsderived from the following dye classes: aminostyryl, anthraquinone,1,4-diamino-2,3 dicarboximideanthraquinone, azo, hydrazone, metal-azo,metal-azo methine, indoaniline, metal formazan, pthalocyanine,naphthaquinone, and nitro dyes. Preferred D groups include1-anthraquinonyl, or 1-(4-substitutedamino)anthraquinonyl. Preferredmetal-containing D groups include organic-derived radical groups fromthe following classes: metal-azo and metal-azo methine dyes, wherein themetal-azo or metal-azo methine ligand is at least bidemate andpreferable tridentate. Preferred metals in the metal-containing D groupsare chromium, cobalt, iron, nickel, palladium, platinum, and copper.When the metal center is chromium, cobalt or iron, it is preferred thanan ancillary ligand such as an alkyldiketonate (for example,acetylacetonate(-1)) or 8-hydroxyquinonlate(-1) is also present in themetal-containing dye fragment. Other preferred classes ofmetal-containing dyes are metal-phthalocyanine or metal formazan dyes.

R⁵ is (Q²)_(p) (D)_(q), wherein Q² and D are defined as above, p is 0 to1 and q is 1 to 10. The bonding atom in R⁵, that is, the atom bonded tothe polymeric chain can be a carbon, nitrogen, sulfur, or oxygen atom.Preferred linking groups (Q²) for R⁵ include --C₆ H₄ NH--, --CONH--,--COO--, --COO(CH₂)_(n) O--, --COO(CH₂)_(n) NH--, where n is 1 to 10.The linking group, Q2 can be attached to a metal-containing dye eitherby coordination to the metal of a metal-containing dye fragment or byformation of a covalent bond to a metallized dye moiety.

a, b, c, d and e independently represent a ratio of a monomeric unit tothe total number of monomeric units of the functionalized portion of theazlactone moieties, such that the sum of a+b+c+d+e equals 1,alternatively, the sum of each of the percents of the single a, b, c, d,and e monomeric units of the total number of monomeric units is equal to100%; preferably a is 0.10-0.99, b is 0.0-0.89, c is 0.0-0.99, d is0-0.99, and e is 0-0.99, with the proviso that the sum of c+d is atleast 0.01, more preferably a is 0.5-0.6, b is 0.1-0.5, c is 0.0-0.5, dis 0-0.5 and e is 0-0.2, with the proviso that the sum of c+d is atleast 0.01.

When the reactive polymeric dye contains an optional additional monomer,the polymer has "e" monomeric units in range of greater than 0 and up to0.89, more preferably in the range of greater than 0 and up 0.2. R⁶ is aunit of the polymer derived from the free radical polymerization of freeradically polymerizable monomers. Such monomers include acrylic andmethacrylic acid, monofunctional acrylates, methacrylates, acrylamide,methacrylamides, acrylonitrile, methacrylonitrile, styrene,N-vinylpyrrolidone and 2-alkenylazlactone. Preferable co-monomersinclude dimethylaminoethyl methacrylate and acrylate, methylmethacrylate, ethyl acrylate, ethylene oxide acrylate, itaconic acid,2-alkenylazlactone, isooctyl methacrylate, lauryl methacrylate, or saltsthereof; preferably quaternary ammonium salts having 4 to 25 carbonatoms, more preferably having 10 to 25 carbon atoms. Examples ofpreferred quaternary ammonium cations include, but are not limited to,ethyl trimethyl ammonium, tetrabutyl ammonium, hexyltributyl ammonium,tetrahexyl ammonium, methyl tribenzyl ammonium, benzyl trimethylammonium, and the like.

The colorant layer formulation may contain various additional adjuvantsin combination with the reactive polymeric dye. Such adjuvants includeplasticizers, photoinitiators, sensitizers, electron donors, coatingaids, multifunctional monomers or oligomers (crosslinking enhancers),antioxidants (e.g., ascorbic acid, hindered phenols, phenidone, etc.) inamounts sufficient to prevent premature crosslinking but insufficient toprevent crosslinking of the reactive polymeric dyes upon exposure toactinic radiation. Leveling agents, wetting agents (such as thosedescribed in U.S. Pat. Nos. 3,787,351 and 4,668,406 and such descriptionis incorporated herein by reference), antistatic agents, waxes,ultraviolet radiation absorbers, mild oxidizing agents, and brightenersmay also be used provided they do not adversely affect the practice ofthe invention. These adjuvants may be added in amounts effective for theknown function of the materials and generally are in the range of 0.01to 10.0 weight % of the colorant layer formulation (100% solids).Preferred total adjuvant weight % is in the range of 0-80 weight %.

The colorant layer formulation is prepared by dissolving the polymers ina suitable solvent to a concentration of about 5-70% by weight,preferably about 10 to 50% by weight. When the polymers have beenprepared in a solvent, it may be necessary only to add additionalsolvent to reach the desired concentration. Examples of solvents thatcan be used include water; ketones, such as, acetone, methyl ethylketone; aqueous and non-aqueous alcohols, such as methanol, ethanol,n-propanol, isopropanol; ethyl acetate; benzene; toluene;trichloroethylene; monomethyl ether of ethylene glycol; propylene glycoland the like. Preferred solvents are water, aqueous alcohols andketones. The dried coating weight of the colorant layer formulation istypically 0.3 to 5 g/m², preferably 0.5 to 4 g/m², and most preferably0.5 to 2.5 g/m².

The colorant layer formulation also contains a photoinitiator that maybe a single Compound or a combination of two or more such compounds thatgenerates radicals upon exposure to actinic radiation. Photoinitiationmay be direct or sensitized. Preferred photoinitiators are sensitized orunsensitized halomethyltriazines (described, for example, in U.S. Pat.No. 3,775,113) and sensitized diaryliodonium salts (described, forexample, in U.S. Pat. Nos. 3,729,313, 4,058,400, 4,058,401, and4,921,827), hereby incorporated herein by reference. Suitablesensitizers for the preferred photoinitiators, along with effectiveamounts of initiator are described in the foregoing references.Effective amounts of initiator are typically in the range of 0.01 to 15weight % of the total polymerizable composition.

Preferred diaryliodonium salts useful as photoinitiators in practice ofthe instant invention may be generally described by the formulas asdescribed in U.S. Pat, No. 4,460,154, that is ##STR9## wherein R¹⁵ andR¹⁶ can be individually selected from aromatic groups having from 4 to20 carbon atoms (e.g., substituted or unsubstituted phenyl, naphthyl,thienyl and furanyl) with substantially any substitution which does notinterfere with the desired reaction,

J is selected from a carbon-carbon bond, oxygen, sulfur, alkylene,arylene, ##STR10## R¹⁷ can be aryl (e.g., 6 to 20 carbon atoms) or acyl(e.g., 2 to 20 carbon atoms), R¹⁸ and R¹⁹ can be independently selectedfrom hydrogen, alkyl groups of 1 to 4 carbon atoms, and alkenyl groupsof 2 to 4 carbon atoms,

D¹⁻ can be any anion, preferably a complex metal halide such ashexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, etc.

Examples of preferred diaryliodonium cations are diphenyliodonium,di(4-chlorophenyl)iodonium, 4-trifluoromethylphenylphenyliodonium,4-ethylphenylphenyliodonium, di(4-acetylphenyl)iodonium,tolylphenyliodonium, anisylphenyliodonium, 4-butoxyphenylphenyliodonium,di(4-phenylphenyl)iodonium, di(carbomethoxyphenyl)iodonium, etc.Examples of other iodonium cations are disclosed in U.S. Pat. Nos.3,729,313, 4,076,705, and 4,386,154.

Examples of substituted halomethyltriazines useful as photoinitiatorsare 2,4-bis(trichloromethyl)-6-methyl-s-triazine,2,4,6-tris(trichioromethyl)-s-triazine, and styryl substituted triazinessuch as 2,4-bis(trichloromethyl)-6-(4'-methoxystyryl)-s-triazine,2,4-bis(trichloromethyl)-6-(p-dimethylaminostyryl)-s-triazine,2,4-bis(trichloromethyl)-6-(2',4'-diethoxystyryl)-s-triazine, etc. Thesecompounds are described as noted above in U.S. Pat. Nos. 3,515,552,3,536,489, 3,617,288, 3,640,718, 3,779,778, 4,386,154, 3,954,475, and3,987,037.

It is also within the scope of the invention to include in the colorantlayer formulation, 0 to 40 parts of a copolymerizable ethylenicallyunsaturated monomers or oligomers per part of the reactive polymericdyes by weight in the polymerization compositions as crosslinkingenhancers. Non-limiting examples of monomers are (meth)acrylic acidesters such as, for example, ethyl acrylate, butyl acrylate, n-octylacrylate, allyl acrylate, cyclohexyl acrylate, N-methylcarbamoyloxyethylacrylate, and multifunctional acrylates and methacrylates such asneopentylglycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritoltriacrylate and tetraacrylate,1,3,5-tri(2-acryloyloxyethyl)isocyanurate, and the correspondingmethacrylates. The preferred multifunctional oligomer is hexafunctionalacrylate as described in U.S. Pat. No. 4,316,949 and such description isincorporated herein by reference.

A transparent binder may optionally be present in the colorant layerformulation. Polymeric binders may be used in the practice of thisinvention. Organic polymeric resins may be used. Thermoplastic resinsare generally preferred. Examples of suitable binders are sulfonatedpolystyrene, polyvinyl alcohol, starch, polymethyl methacrylate,polyvinyl acetate, and the like. Beyond this minimal requirement oftransparency, there is no criticality in the selection of a binder. Agenerally useful range is up to 30 percent by weight binder, preferably2 to 15 percent of binder by weight.

Support base films used in the present invention support the colorantlayer developable by an aqueous developing solution, thus fixing each ofthe layers and enabling each of the layers to exert its respectivefunction. The support base film also provides the colorant layer withmechanical strength and dimensional stability in the temperature rangebetween about 0° C. to about 200° C. The term "transparent" support asused herein means supports having a thickness of from about 50micrometers to about 2 millimeters, and more preferably from about 80micrometers to about 1.5 millimeters, which can transmit not less thanabout 65%, of incident light with a wavelength of from about 290nanometers to about 700 nanometers. When the color proofing constructionis used for a surprint application or a transfer lithographicapplication, the support base material need not be transparent, butshould provide a release surface, which may either be a smooth surface,or a surface coating thereon.

Suitable support base films include resin-coated paper, aluminumsheeting, or various transparent opaque plastic sheets or films.Suitable transparent or opaque plastic sheets or films include filmforming synthetic or high polymers including cellulose nitrate,cellulose acetate, cellulose acetate butyrate, cellulose acetatepropionate, polystyrene, polyester, e.g., poly(ethylene terephthalate),poly(vinylidene chloride), poly(vinyl chloride), polypropylene,poly(vinyl acetate), polyisobutylene polymers and copolymers,polycarbonate, etc., and various laminated films of the above describedmaterials. Among these, the preferred support material is a flexiblepoly(ethylene terephthalate) film.

The adhesive layer comprises a thermally activated adhesive that may becoated on the top surface of a barrier layer or the colorant layer. Thecoating thickness of this layer is generally 5 to 20 g/m². A thermallyactivated adhesive layer is preferred over a pressure sensitive adhesivebecause the thermally activated adhesive can be positioned andrepositioned (before lamination) without a chance of altering thereceptor surface or picking up extraneous matter as can occur withpressure sensitive adhesive layers. The physical nature of a smooth,transparent and optically clear thermally laminable adhesive layeroffers better optical qualities than a pressure sensitive adhesivelayer.

The thermally activated adhesive layer preferably provides the followingproperties:

(1) thermal laminability at a temperature below 200° C., preferablybetween 100° to 160° C., at a pressure of 1.6 lb/in² (0.29 kg/cm²),

(2) non-tacky at room temperature or preferably not laminable to paperor self-laminable at 45° C. and 60° C., 2 g/cm², for at least one week,

(3) will not discolor or alter its optical density by more than 0.05optical density units when an area of 15,000 cm² is exposed to a 5 kWsource of UV radiation having a majority of the radiation distributedover the range of 350 to 450 nm, at a distance of 1 meter for 2 minutes,and

(4) have no ingredients which by themselves or in combination with thesolvent of the adhesive layer migrate across a barrier layer anddesensitize the colorant layer, or alter the optical qualities of thebarrier or colorant layer.

Nonlimiting examples of useful thermal adhesive systems are acrylatepolymers and copolymers with a laminating temperature in the range of100° C. to 160° C. at a pressure of 1.6 lb/in² (0.29 kg/cm²) for 5-10seconds and nonexclusively include n-butyl acrylate, ethyl acrylate,isopropyl acrylate and their copolymers with ethylenically unsaturatedmonomers such as other acrylates, acrylic anhydride, acrylic acid,methacrylic acid, styrene, vinyl acetate, and the like. Any monomersthat cause yellowing or discoloration when exposed to 5 kW UV radiationat about 417 nm at 1 meter for two minutes should be avoided.

Optionally, a barrier layer can be added to the color proofingconstruction when preparing a single sheet proofing construction. Thiscan be accomplished by adding the barrier layer between the colorantlayer and the adhesive layer, wherein the barrier layer is farther awayfrom the support base film than the colorant layer. Optical transparencybetween 100° C. and 160° C. are required. Beyond these minimalrequirements, there is no criticality in the selection of the barrierlayer composition. Suitable examples that can be used in this inventioncan be an aqueous developable functional material or an aqueousinsoluble non-functional material or a mixture thereof. The thickness ofthe barrier layer may generally range from about 0.1 g/m² to about 0.3g/m² (0.1 μm to 0.3 μm).

Since many photopolymerizable constructions utilizing free radicalpolymerization are affected by oxygen, an oxygen barrier layer is usedto protect the colorant layer containing the reactive polymeric dye.Advantageously, the reactive polymeric dyes used in the presentinvention are relatively oxygen insensitive, thus requiring no oxygenbarrier. However, an optional oxygen barrier layer is within the scopeof the present invention. Such an oxygen barrier layer comprisespolyvinyl alcohol, polyvinyl pyrrolidone or mixtures thereof. The oxygenbarrier layer is typically positioned adjacent to at least one majorsurface of the colorant layer, that is, the oxygen barrier layer may bebetween the support base film and the colorant layer, if the supportbarrier layer is removeable, or the oxygen barrier layer may overlay thecolorant layer on the surface away from the support base film.Transparency and satisfactory oxygen impermeability properties between20° C. and 50° C. are required. Beyond these minimal requirements, thereis no criticality in the selection of the oxygen barrier layercomposition and such layers as known in the art are within the scope ofthe present invention.

METHOD OF USE

Fundamentally, two basic methods of development of a photoresist systemcan be described, these being chemical and mechanical development.Chemical development involves the swelling and solubilizing of eitherthe unpolymerized photodegraded portions of the resist. Mechanicaldevelopment incorporates an image forming layer or sheet which interactseither with the exposed or unexposed regions such that upon mechanicalexertion, such as peeling, an image is formed on both the base layer andthe image forming layer. These images can either be positive or negativeimages for the base layer depending on the photosensitive properties ofthe image forming layer.

In preparing a color proof, a transparent color proofing construction isprovided for each of the colors to be printed. Each of the colorconstructions is exposed through its respective color separationnegative. Upon processing, the color in the non-image areas is removed,yielding a sheet that contains the desired color pattern in the imageareas, while being colorless and transparent in the non-image areas,otherwise producing a negative imaging system. After the separatecolored images are made, they are assembled together in registry on awhite or otherwise suitable colored background matching the surface onwhich printing is to occur. Processing may include art known aqueous ormay be art known dry peel apart techniques.

In preparing a surprint, the colors are processed individually andconsecutively. A sheet of the color represented by the first negative tobe proofed, for example yellow is prepared for processing by laminatingthe color sheet to a backing sheet. Pressure applied by conventionallaminating apparatus with a heated roller is sufficient to achievelamination through the thermally laminable adhesive. Followinglamination, the support base film is stripped away. The colorant layernow on the backing sheet is contact exposed through the correspondingcolor separation negative.

The light imaged backing is then physically developed with an aqueousdeveloping solution, brushing and wiping with a soft cloth pad to removethe reactive polymeric dye and unexposed colorant layers from thenon-image (unexposed) areas to leave the latter clear and colorless.Thereby a negative image is defined, faithfully representing thereproduction and full color range which would result if the completeplatemaking and printing operation (using appropriately matched ink)were carried through with that color separation negative.

A sheet of second color to be proofed, for example, magenta, is preparedin the same way by laminating it to the yellow imaged backing sheet. Thecorresponding color separation negative must now be positioned in exactregister with the yellow image. This is commonly provided for by apreregistration of all the separation negatives and the backing sheet bya system of register marks or punches. The colorant layer (magenta) nowon the yellow-imaged backing sheet is exposed and processed, as for thefirst color (yellow). The remaining cyan and black images are thereafteradded, in turn, thus reproducing the four color negative result thatwould occur in printing, were printing plates employed prepared from thesame color separation negatives.

Certain relationships should exist between the elements of the colorproofing construction just described. Adhesive relationships must besuch that, after adhesive lamination to the backing sheet, the releasesurface will allow stripping away the support base film withoutdisrupting the adhesive bond. Failure must not occur at either theadhesive-backing sheet or adhesive-barrier layer bonds. When the releasesurface is provided by a surface coating on the support base film, it isnot particularly critical whether release occurs between support basefilm-release layer or release layer-colorant layer. However, release isgenerally less efficient between two in situ formed layers and resultsin somewhat more likely release between the support base film and therelease layer. In this event, it is of importance that the release layerbe transparent and soluble in the aqueous developing solution.

The color proofing construction of the present invention is exposedimagewise to .actinic light. Preferably, the wavelength of the actiniclight used at the wavelength of maximum sensitivity of the colorantlayer. The imagewise exposure can be carried out using known methods forlight sensitive materials. Examples of suitable light sources which canbe employed are a high pressure mercury are lamp, a ultra-high pressuremercury are lamp, a carbon are, a xenon are lamp, a laser, a tungstenfilament incandescent lamp, a luminescent discharge tube, a cathode raytube, sunlight, etc. The intensity of the actinic light is selected sothe exposure time is in the range of from about 0.1 seconds to about 1minutes, and more preferably from about 0.5 to about 15 seconds. Otheruseful light sources include various lasers, that is, argon ion, diode,excimer, and dye lasers. In the case of lasers, the exposure times aredependent upon the spatial distribution of the laser beam and power ofthe lasers.

After imagewise exposure, the color proofing construction is processedusing an aqueous developing solution, wherein the unexposed portions ofthe colorant layer are dissolved away in the aqueous developing solutionor using a dry peeling process, wherein the unexposed portions of thecolorant layer are adhered to the dry peel receptor. The remainingareas, that is, the exposed areas of the colorant layer and the adhesivelayer (if present) constitute a negative image.

The term "aqueous developing solution" as employed in the description ofthe present invention means water per se, mixtures of water andwater-miscible organic solvents, water containing an alkaline compound,and mixtures of water, water-miscible organic solvents and an alkalinecompound. Useful water-miscible organic solvents form a homogenous phasewhen mixed with water in particular ratios of about 50% by volume orless, preferably about 25% by volume or less and more preferably about5% by volume or less of the organic solvent to the total volume of themixture. Such suitable water-miscible organic solvents include aliphaticalcohols containing up to 6 carbon atoms, for example, methanol,ethanol, propanol, butanol, 2-propanol, t-butyl alcohol, isoamylalcohol, and 1-hexanol. Suitable alkaline compound that can be usedinclude sodium hydroxide, potassium hydroxide, lithium hydroxide, sodiumphosphate, potassium phosphate, sodium carbonate, potassium bicarbonate,sodium carbonate, potassium bicarbonate, sodium meta-silicate, andpotassium silicate. Preferably, the aqueous developing solution iswater, sodium bicarbonate, potassium carbonate mixed with a suitablesurfactant, such as SURFYNOL (Union Carbide).

Regardless of the presence of the water-miscible organic solvent, theamount of the alkaline compound in the aqueous developing solutionshould not exceed about 20% by weight, and more preferably should befrom about 0.5 to 10% by weight, of the total amount of the aqueousdeveloping solution. The pH should range from about 7 to about 13.5,which shifts to about 7 to about 12 or to a pH in the range of 7 to 11when a water-miscible organic solvent is present.

The developing solution can also contain a surface active agent [such asthose described in J. Grant, Ed. Hackh's Chemical Dictionary, 4th Ed.,McGraw-Hill Book Co., New York (1969)].

While aqueous development generally provides a negative image colorproofing construction, the reactive polymeric dyes can also be used indry peel-apart positive image color proofing constructions, such as maybe known in the art.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. All materialsare commercially available or known to those skilled in the art unlessotherwise stated or apparent. M_(n) is the number average molecularweight.

    ______________________________________                                        Glossary                                                                      ______________________________________                                        ASATBA  aspartic acid tetrabutylammonium salt (as prepared                            in Example 23)                                                        BHT     2,6-di-tert-butyl-4-methylphenol (commerically avail-                         able from Aldrich)                                                    DBU     1,8-diazabicyclo[5.4.0]undec-7-ene (commerically                              available from Aldrich)                                               HEMA    2-hydroxyethylmethacrylate (commerically available                            from Sartomer)                                                        MEK     2-butanone, also known as methyl ethyl ketone                                 (commercially available from Aldrich)                                 PVA     polyvinyl alcohol                                                     UGRA    Target Plate Control Wedge (commerically avail-                               able from Ugra, St. Gall, Switzerland                                 VAZO-64 2,2'-azobis(2-methylpropionitrile) (commerically                              available from DuPont)                                                ______________________________________                                    

EXAMPLES PREPARATION OF MATERIALS

The 4-aminostyrene was obtained from Johnson Matthey, Alfa Products, 30Bond Street, Ward Hill, Mass. 01835. ¹ H NMR of this sample showed thatit contained 3-5% 4-ethylaniline. The dye derivatives of 4-ethylanilineand 4-aminostyrene were not separated.

EXAMPLE 1

This example describes the preparation of a chromium complex of thedoubly deprotonated dianion of[2-[N-(2-hydroxy-3,5-dinitrophenyl)forminidoyl]-3,5-dimethoxy] phenol(1), a yellow dye precursor. ##STR11##

Compound 1 was prepared using procedures described in U.S. Pat. No.3,597,200. In a 250 ml two-neck flask equipped with a Dean-Stark trapand reflux condenser were placed chromium(III) chloride hexahydrate(4.00 g, 0.015 mol), 40 ml dimethyl formamide, and 50 ml toluene. Thecontents of the flask were heated with separation of water as atoluene/water azeotrope. Next, 100 ml isopropanol was added followed byheating to remove the toluene as a isopropanol/toluene azeotrope. Afterapproximately 150 ml distillate was collected, the flask was cooled and2-hydroxy4,6-dimethoxybenzald(2'-hydroxy-5'-nitrophenyl)imine (4.77 g,0.015 mol) was added. The reaction mixture was then heated at 90° C. forhours. The solution was cooled to 60° C. and 2,4-pentanedione (1.54 ml,0.015 mol) and tri-n-butylamine (3.57 ml, 0.015 mol) were added andheating was continued for another 2.5 hours. The mixture was cooled andthen poured into a total of 800 ml distilled water containing severaldrops concentrated hydrochloric acid. The resulting yellow-brown solidwas dried in vacuo to afford 4.78 grams of compound 1 (58% yield);λ_(max) (methanol)=460, 435, 405, 380, 328, 321, 309 nm.

EXAMPLE 2

This example describes the preparation of[2-[N-(2-hydroxy-3,5-dinitrophenyl)forminidoyl]-3,5-dimethoxy] phenol(2), a yellow free-radically polymerizable dye. ##STR12##

Into a 50 ml round bottom flask were placed compound 1 (0.666 g, 1.4mmol), followed by 25 ml methylene chloride. To this solution was added4-vinylpyridine (0.74 ml, 6.8 mmol), with continued stirring for 12hours. The progress of this reaction was conveniently followed by thinlayer chromatography. The reaction solvent was then removed under vacuumand the resulting residue washed with two portions of petroleum ether.Drying the sample under vacuum afforded 0.776 gram (98% yield) ofcompound 2 as a red-brown solid that was recrystallized from methylenechloride/hexane; m.p. 230° C. (dec); λ_(max) (methanol): 439 nm(ε=14,100M⁻¹ cm⁻¹), 405 nm (ε=14,700 M⁻¹ cm⁻¹), 381 nm (ε=14,600 M⁻¹cm⁻¹), 323 nm (ε=14,600 M⁻¹ cm⁻¹).

EXAMPLE 3

This example describes the preparation ofaqua[4-[(N,N-dibutylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](2,4-pentanedionato-O,O')chromium(3), a magenta precursor. Note: "Ph" designates a phenyl group.##STR13##

Into a 200 ml round bosom flask were placedN,N-dibutyl-3-hydroxy-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)azo-1-naphthalenesulfonamide(5.36 g, 10.0 mmol), chromium(III) chloride hexahydrate (3.46 g, 13.0mmol), and 50 ml of dimethyl formamide. The reaction mixture was thenheated at 130° C. for 3 hours. The resulting magenta reaction mixturewas cooled to 95° C. and 2,4-pentanedione (1.54 ml, 15.0 mmol) andtri-n-butylamine (3.57 ml, 15.0 mmol) were added. After stirring at thistemperature for 1.5 hours the reaction mixture was cooled to 25° C. andpoured into 300 ml of distilled water containing several drops of conc.hydrochloric acid. The product was collected by vacuum filtration washedextensively with distilled water, and dried under vacuum to afford 7.20g (100% yield) of compound 3; λ_(max), (methanol)=557, 522 nm.

EXAMPLE 4

This example describes the preparation of[4-[(N,N-dibutylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](4-ethenylpyridine)(2,4-pentanedionato-O,O')chromium(4), a magenta free radically polymerizable dye. ##STR14##

Into a 100 ml round bottom flask were placed compound 3 (1.02 g, 1.3mmol) and 50 ml of methylene chloride. To this stirred solution wasadded 4-vinylpyridine (0.43 ml, 4.0 mmol). After stirring for 24 hoursthe solvent was removed under vacuum to afford a magenta gum. The gumwas triturated by adding several portions of hexane and scraping thesides of the flask. The resulting solid was collected by vacuumfiltration and dried under vacuum to afford 1.12 grams (100% yield) ofcompound 4. The sample was recrystallized from a mixture of toluene,methylene chloride, and heptane to give magenta crystals; m.p. 167° C.;λ_(max), (methanol)=568, 532 nm.

EXAMPLE 5

This example describes the preparation ofaqua[4-[(N,N-dibutylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](2,4-pentanedionato-O,O')chromium(5), a magenta precursor. ##STR15##

Into a 200 ml round bottom flask were placedN,N-dimethyl-3-hydroxy-4-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)azo-1-naphthalenesulfonamide(3.70 g, 9.1 mmol), chromium(III) chloride hexahydrate (3.15 g, 11.8mmol), and 40 ml of dimethyl formamide. The reaction mixture was thenheated at 130° C. for 3 hours. The resulting magenta reaction mixturewas cooled to 90° C. and 2,4-pentanedione (1.4 ml, 13.7 mmol) andtri-n-butylamine (3.3 ml, 15.0 mmol) were added. After stirring at thistemperature for 1.5 hours the reaction mixture was cooled to 25° C. andpoured into 500 ml of distilled water containing several drops of conc.hydrochloric acid. The product was collected by vacuum filtration,washed extensively with distilled water, and dried under vacuum toafford compound 5 as a magenta powder.

EXAMPLE 6

This example describes the preparation of[4-[(N,N-dimethylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](4-methylcarbinolpyridine)(2,4-pentanedionato-O,O')chromium(6), a nucleophilic magenta dye. ##STR16##

Into a 200 ml single-neck flask were placed compound 5 (3.00 g, 4.85mmol) and 4-pyridylcarbinol (1.48 g, 13.6 mmol). To this was added 70 mlof methylene chloride and the reaction mixture stirred at 25° C. forovernight. Acetone (15 ml) was then added with continued stirring forseveral days at 25° C. The solvent was removed under vacuum and theresulting residue recrystallized from hot toluene/methanol to affordcompound 6 as magenta crystals. λ_(max), (methanol)=566.5, 531 nm.

Other useful polymerizable metal-azo and metal-azo methine dyes aredescribed in U.S. Pat. No. 5,166,326 and such description isincorporated herein by reference.

EXAMPLE 7

The tetrahydropyranyl derivative of 1-bromopropanol was preparedaccording to J. Am. Chem. Soc. 1972, 94, 6751.

This example describes the preparation of the 3-tetrahydropyranylderivative of 1,4-diaminoanthraquinone-2,3-dicarboximide (7), a cyanprecursor. ##STR17##

Into a 250 ml flask were placed 1,4-aminoanthraquinone-2,3-dicarboximide(4.824 g, 15.7 mmol) (BASF, Aktiengesellschaft D-6700 Ludwigshafen/RFWest Germany) and 150 ml of anhydrous DMF. To this stirred solution at25° C. was added potassium t-butoxide (95%) (1.81 g, 18.8 mmol) in smallportions. After the addition was complete stirring was continued for 1hour at 50° C. The tetrahydropyranyl derivative of 1-bromopropanol (5.86g, 26.3 mmol) in 10 ml of anhydrous DMF was the added dropwise to thereaction mixture. The viscous solution was then stirred for about 24hours at 50° C. The solution was cooled to 25° C. and then poured into 1liter of distilled water. The resulting dark blue precipitate wascollected by vacuum filtration and washed with several portions ofdistilled water. The solid material was then subjected to Soxhletextraction using methylene chloride. Removal of the methylene chloridesolvent under vacuum gave compound 7 as a deep blue solid. The ¹ H NMRspectral data of this sample was consistent with its assigned structure.

EXAMPLE 8

This example describes the preparation of the 3-propanol derivative of1,4-diaminoanthraquinone-2,3-dicarboximide (8), a nucleophilic cyan dye.##STR18##

Into a 500 ml flask were placed compound 7 (2.70 g, 6.0 mmol), 110 ml ofmethanol, 20 ml of distilled water, and 1.5 ml of cone. sulfuric acid.The reaction mixture was then refluxed for overnight. The solution wascooled to 25° C. and the resulting dark blue solid collected by vacuumfiltration and washed with several portions of methanol. After dryingunder vacuum compound 8 was obtained in quantitative yield. The ¹ H NMRand mass spectral data of this sample were consistent with its assignedstructure.

EXAMPLE 9

This example describes the synthesis of1-(1-methylpropylamino)anthraquinone (MPAQ) (9), a free-radicalpolymerizable cyan precursor. ##STR19##

A Parr stainless steel high pressure reactor was charged with 24.26grams (0.10 moles) of 1-chloroanthraquinone, 14.13 g (0.19 moles) ofsec-butylamine, 13.05 grams (0.133 moles) potassium acetate, 0.66 gram(0.01 moles) of activated copper metal, 0.03 gram (2 mmoles) of water.The reaction vessel was sealed and heated to 180° C. in an oil bath for12 hours. The oil bath was removed and the vessel was allowed to returnto ambient condition. The solid was extracted with methylene chlorideand the insoluble materials removed by filtration. The solvent wasremoved and the solid was recrystallized from hot methanol. The crudeyield of compound 9 was 84%. The material was chromatographed on asilica gel column using toluene as the eluent. Melting point was136°-138° C. Absorption maximum was observed at 515 nm in methylenechloride.

EXAMPLE 10

This example describes the synthesis of1-(1-methylpropylamino)-4-bromoanthraquinone (BMPAQ) (10), afree-radically polymerizable cyan precursor. ##STR20##

MPAQ (20.02 g, 0.072 moles) was dissolved in hot acetic acid. In aseparate flask, 12.03 g (0.752 mmole) of bromine was dissolved in about10 ml of acetic acid. The bromine solution was slowly added to the dyesolution. The reaction was allowed to proceed for 0.5 hour, withoccasional shaking. The reaction mixture was poured into 600 ml of waterand aqueous sodium sulfite was added to discharge the bromine. Theaqueous solution was decanted off. The solid was dissolved in methylenechloride and then concentrated and slowly added to cold methanol whereupon a solid precipitated. The yield was 21.76 grams (85%) of compound10. Absorption maximum was observed at 515 nm in methylene chloride.

EXAMPLE 11

This example describes the synthesis of1-(1-methylpropylamino)4-(4-styrylamino)-anthraquinone (11), afree-radically polymerizable cyan dye. ##STR21##

A 100 mL round bottom was charged with 3.0 grams (8.4 mmoles) of BMPAQ(10) 1.5 grams, (12.6 mmoles) of 4-aminostyrene 2.0 grams (20.4 mmoles)of potassium acetate 0.2 gram (1.1 mmoles) of copper(II) acetatemonohydrate, and 12 ml of nitrobenzene. The mixture was refluxed for 1hour. By TLC, some starting material was still present, however, a darkblue low R_(f) spot was also apparent, presumably, a polymeric material.The solvent was removed by vacuum distillation and the material wasdissolved in toluene and then filtered. The filtrate was chromatographedon a silica column using toluene as the eluent. The starting materialcame off before the desired product. A higher purity sample was preparedby recrystallizing the material from methylene chloride/methanol,followed by chromatography. The absorption maximum was observed at 651nm in methylene chloride. The melting point was 142° C. ¹ H NMR (CD₂Cl₂) d 12.26 (brs, 1H), 10.88 (brs, 1H), 8.32 (m, 2H), 7.72 (m, 2H),7.63 (d, J=9.5 Hz, 1H), 7.45 (d, J=8.2 Hz, 2H), 7.22 (m, 3H), 6.73 (dd,J=17.6 Hz, 10.9 Hz, 1H), 5.73 (d, J=17.6 Hz, 1H), 5.22 (d, J=10.7 Hz,1H), 3.73 (brm, 1H), 1.71 (m, 2H) 1.32 (d, J=6.35 Hz, 3H), 1.02 (t,J=7.4 Hz, 3H).

EXAMPLE 12

This example describes the synthesis of 1-(4-styrylamino)anthraquinone(STYAQ) (12), a flee-radically polymerizable magenta dye. ##STR22##

Into a 100 ml round bottom equipped with a reflux condenser and wasadded 3.5 grams of 1-chloroanthraquinone, 2.5 grams of 4-aminostryene,2.6 grams of potassium acetate, 0.15 gram of copper(II) acetatemonohydrate, 17 ml of nitrobenzene. The above mixture was refluxed for50 minutes under a nitrogen blanket. By TLC most of the startingmaterial was gone and some low R_(f) material was apparent. The solventwas removed by vacuum distillation. The solid was extracted with tolueneand chromatographed on a silica column using toluene as an eluent. Twodark red fractions were collected, the less polar fraction was1-(4-styrylamino)anthraquinone (STYAQ) (12). The more polar red fractionwas a 4-aminostyrene addition product to STYAQ, where the amine is addedto the benzylic position. The melting point of STYAQ is 174° C. Theabsorption maximum is 512 nm in methylene chloride. ¹ H NMR (CD₂ Cl₂) d11.34 (s, 1H), 8.25 (m, 2H), 7.76 (m, 2H), 7.67 (dd, J=7.0 Hz, 1.4 Hz,2H), 7.43 (m, 4H), 7.28 (d, J=8.4 Hz, 2H), 6.73 (dd, J=11.0 Hz, 17.6 Hz,1H), 5.74 (d, J=17.6 Hz, 1H), 5.24 (d, 10.7 Hz, 1H). The additionproduct structure was determined by proton NMR and confirmed by lasermass spectroscopy. Negative-ion laser desorption revealed a parent ionpeak at m/z 444 mass units, the most intense feature was at m/z 325,corresponding to loss of an aminostryene (NH₂ C₆ H₄ C₂ H₃). Thepositive-ion laser desorption spectrum shows a molecular ion at m/z at326 corresponding to a loss of the aminostyryl radical (NHC₆ H₄ C₂ H₃),but no parent ion. The maximum absorption of the addition product wasobserved at 511 mn methylene chloride. ¹ H NMR (CD₂ Cl₂), d 11.32 (s,1H), 8.29 (dd, J=7.6 Hz, 1.6 Hz, 1H), 8.22 (dd, J=7.4 Hz, 1.6 Hz, 1H),7.77 (m, 2H), 7.65 (dd, J=6.3, 2.1 Hz, 1H), 7.48 (m, 2H), 7.41 (d, J=8.4Hz, 2H), 7.28 (d, J=8.4 Hz, 2H), 7.1 (d, J= 8.6 Hz, 2H), 6.56 (dd,J=17.6 Hz, 10.9 Hz, 1H), 6.50 (d, J=8.6 Hz, 2H), 5.48 (d, J=17.6 Hz,1H), 4.97 (d, J=10.9 Hz, 1H), 4.54 (q, J=6.6 Hz, Hz, 4.27 (brs, 1H),1.54 (d,J=6.7 Hz, 3H).

EXAMPLES 13-14

This example describes the synthesis of1-(2-aminoethylamino)anthraquinone (13) and1-(3-aminopropylamino)anthraquinone (14), magenta nucleophilic dyes.##STR23##

These were prepared by a modification of a literature procedure for1-(2-aminoethylamino)anthraquinone where an excess of the amine wasreacted with 1-chloroanthraquinone, instead of 1-nitroanthraquinone, andthe mixture refluxed for 20 min (U.S. Pat. No. 2,888,379). Thestructures were confirmed by ¹ H NMR spectroscopy. The propyl derivativehad an absorption maximum at 510 nm and the ethyl derivative had amaximum at 505 nm in methylene chloride.

EXAMPLES 15-23

Examples 15-23 described the synthesis of reactive macromolecular dyes,either incorporating free radically polymerizable dyes into the backbonevia copolymerization with azlactone (Examples 15, 17-18, and 21-23) orincorporating the dyes pendent to the polymerized azlactone backbone(Examples 16, and 19-20).

In the following examples, the portion of the macromolecular dyedescribed by: ##STR24## will be conveniently represented by thefollowing: ##STR25##

EXAMPLE 15

This examples describes the synthesis of a reactive copolymeric yellowdye: ##STR26##

Into a vessel 18.0 parts by weight of azlactone monomer, 2.0 parts byweight of a 1-methacrylamido-anthraquinone (a yellow dye) prepared usinga slight modification of a literature procedure (GB Patent No. 1,06,700)(modification involved heating 1-aminoanthraquinone in o-dichlorobenzenesolution to about 140°-150° C. prior to addition of the sodiumcarbonate), 0.40 parts by weight of VAZO-64 and 40 parts by weight ofMEK were charged. The solution was purged with nitrogen for 10 minutes.The vessel was sealed and put into a constant temperature bath andheated at 65° C. for 20 hours. Solids analysis revealed a quantitativereaction (no detectable monomer remained) to afford the yellowcopolymer.

Into the vessel 0.49 parts by weight of DBU, 8.42 parts by weight of MEKand 0.11 parts by weight of BHT were added. To this mixture 8.42 partsby weight of HEMA and 8.42 parts by weight of MEK were added. Thesolution was heated at 50° C. for 1 hour. An infrared (IR) spectrumanalysis revealed a complete reaction to afford the HEMA adduct.

Into the vessel 4.84 parts by weight of ASATBA (as prepared in Example24) in 9.69 parts by weight of MEK were added and the solution wasstirred for 30 minutes. Then 0.40 parts by weight of DBU, 0.04 parts byweight of BHT and 3.74 parts by weight of deionized water were added.The solution was heated at 50° C., after 11 hours an IR spectrumanalysis revealed a complete reaction to afford the reactive copolymericyellow dye.

EXAMPLE 16

This examples describes the synthesis of reactive polymeric cyan dye:##STR27##

Into a vessel 351.0 parts by weight of azlactone monomer, 7.0 parts byweight of VAZO-64 and 702.0 parts by weight of MEK were charged. Thissolution was purged with nitrogen for 10 minutes and the solution washeated to 60° C. for 3 hours. The temperature of the solution was raisedto 80° C. and held at this temperature for 2 hours. Solids analysisrevealed a quantitative reaction to afford an azlactone homopolymerwithout any detectable remaining monomeric azlactone.

Into a vessel 21.08 parts by weight of the above azlactone polymersolution, 0.17 parts by weight of DBU and 2.85 parts by weight of MEKwere charged. To this a premix of 2.85 parts by weight of HEMA, 0.04parts by weight of BHT and 2.85 parts by weight of MEK were added. Thereaction was heated at 50° C. for 1 hour.

1,4-Diaminoanthraquinone-2,3-dicarbonylimide (a blue dye preparedaccording to Example 8) (1.94 parts by weight in 3.88 parts by weight ofMEK) was added to the flask and the mixture was heated at 50° C. for 1hour.

Then 2.05 parts by weight of ASATBA dissolved in 4.10 parts by weight ofMEK were added. The mixture was heated at 50° C. for 1 hour.

Into the vessel 0.17 parts by weight of DBU and 0.80 parts by weight ofdeionized water and 0.017 parts by weight of BHT were added. The mixturewas heated at 50° C., after 11 hours IR spectrum analysis revealed aquantitative reaction to afford the reactive polymeric cyan dye.

EXAMPLE 17

This example describes the synthesis of a reactive copolymeric yellowdye: ##STR28##

Into a vessel 5.0 parts by weight of alkenylazlactone monomer, 2.65parts by weight of a 1-methacrylamido-anthraquinone (a yellow dye)prepared using a slight modification of a literature procedure (GBPatent No. 1,036,700) (modification involved heating the1-aminoanthraquinone in o-dichlorobenzene solution to about 140°-150°C., prior to addition of the sodium carbonate), 0.15 parts by weight ofVAZO-64 and 30.1 parts by weight of tetrahydrofuran (THF) were charged.The solution was purged with nitrogen for 5 minutes. The vessel wassealed and placed in a constant temperature water bath at 65° C. for 20hours. A percent solids determination indicated a quantitativeconversion to afford a yellow copolymer.

To this mixture 0.109 parts by weight of DBU. 0.01 parts by weight ofBHT and 1.87 parts by weight of HEMA were added. The vessel was heatedat 50° C. for 30 minutes, then 1.34 parts by weight of ASATBA dissolvedin 1.3 parts by weight of THF were added and stirred at 30° C. for 2hours.

Then 0.14 parts by weight of DBU and 1.29 parts by weight of deionizedwater were added to the vessel. The reaction solution was heated for 4hours at 40° C. in a constant temperature water bath. IR analysisindicated a quantitative reaction to afford the reactive copolymericyellow dye.

EXAMPLE 18

This example describes the synthesis of a reactive polymeric magentadye: ##STR29##

Into a vessel 100 parts by waist of azlactone monomer, 2.0 parts byweight of VAZO-64 and 200 parts by waist of MEK were charged. Thesolution was purged with nitrogen for 10 minutes. The vessel was sealedand placed in constant temperature water bath at 65° C. for 20 hours. Aviscous poller solution was obtained. A percent solids analysisindicated a quantitative reaction to afford an azlactone homopolymer.

A flask was fitted with a condenser, a magnetic stirrer and athermometer and was charged with 2.31 parts by weight of the abovepolymer solution. A solution consisting of 0.51 parts by weight of[4-[N,N-dimethylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](4-methylcarbinolpyridine)(2,4-pentanedianato-O,O')chromium(a magenta dye prepared in Example 6) dissolved in 3 parts by weight ofMEK were added to the flask and 0.010 parts by weight of DBU was added.The reaction solution was heated at 50° C. for 2 hours. The flask wascooled to room temperature and 0.265 parts by weight of HEM& 0.01 partsby weight of BHT and 0.265 parts by weight of MEK were added. Thesolution was heated at 50° C. for 2 hours. Then 0.20 parts by weight ofASATBA dissolved in 0.60 parts by weight of MEK was added and thesolution was heated at 50 ° C. for 1 hour. To the flask was added 0.16parts by weight of deionized water and 0.005 parts by weight of DBU. Thesolution was heated at 50° C. for 11 hours. An IR analysis indicatedquantitative reactions.

EXAMPLE 19

This example describes the synthesis of a reactive polymeric magentadye: ##STR30##

Into a vessel 100 parts by weight of alkenylazlactone monomer, 2.0 partsby weight of VAZO-64 and 200 parts by weight of MEK were charged. Thesolution was purged with nitrogen for 10 minutes. The vessel was sealedand placed in a constant temperature water bath at 65° C. for 20 hours.A viscous polymer solution was obtained. A percent solids analysisindicated a quantitative reaction to afford an azlactone homopolymer.

To 31.0 parts by weight of the above solution 0.25 parts by weight ofDBU, 0.01 parts by weight of BHT and 8.62 parts by weight of MEK wereadded. Then 4.31 parts by weight of HEMA were added. The solution washeated for 2 hour at 50° C.

Into the vessel 0.98 parts by weight of1-(2-aminoethylamino)anthraquinone (a dye prepared in Example 13) in 7.0parts by weight of MEK were added. The mixture was stirred for 30minutes. Then 2.76 parts by weight of ASATBA in 5.52 parts by weight ofMEK were added. To this solution 0.25 parts by weight of DBU and 1.06parts by weight of deionized water were added. The solution were heatedfor 19 hours at 50° C. An IR analysis indicated a quantitative reaction.

EXAMPLE 20

This example describes the synthesis of a reactive copolymeric yellowdye: ##STR31##

Into a vessel 9.1 parts by weight of alkenylazlactone, 1.0 parts byweight of[6-[[(2-hydroxy-5-nitrophenyl)imino]methyl]-3,5-dimethoxyphenolato-N,O,O'](4-ethenylpyridine)(2,4-pentanedionato-O,O')chromium(a yellow free-radically polymerizable dye prepared in Example 2), 0.2parts by weight of VAZO-64 and 40 parts by weight of MEK were charged.The solution were purged with nitrogen for 10 minutes. The vessel weresealed and placed in a constant temperature water bath at 65° C. for 20hours. A percent solids analysis indicated a quantitative conversion toafford a yellow copolymer.

To 30.0 parts by weight of the above polymer solution 0.15 parts byweight of DBU, 0.020 parts by weight of BHT and 5.10 parts by weight ofMEK were added. Then 2.55 parts by weight of HEMA was added to thevessel. The solution were stirred at 50° C. for 1 hour.

A solution of 1.47 parts by weight of ASATBA dissolved in 2.93 parts byweight of MEK was added to the vessel. The solution were stirred for 1hour. Then 0.15 parts by weight of DBU and 1.12 parts by weight ofdeionized water were added to the vessel. The solution were heated at50° C. for 20 hours. An IR spectrum analysis indicated a quantitativereaction to afford a reactive copolymeric yellow dye.

EXAMPLE 21

This example describes the synthesis of a reactive copolymeric magentadye: ##STR32##

Into a vessel 9.0 parts by weight of alkenylazlactone monomer, 1.0 partsby weight of[4-[(N,N-dibutylaminosulfonyl-2-hydroxy-1-naphthalenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-onato(-2)](4-ethenylpyridine)(2,4-pentanedionato-O,O')chromium(a dye prepared in Example 4), 0.2 parts by weight of VAZO-64 and 20parts by weight of MEK were charged. The solution was purged withnitrogen for 10 minutes. The vessel was sealed and placed in a constanttemperature water bath at 60° C. for 24 hours. A viscous polymersolution was obtained. A percent solid analysis indicated a quantitativeconversion to afford a magenta copolymer.

Into a vessel, the following components were added: 15 parts by weightof the above copolymer solution, 0.12 parts by weight of DBU, 0.04 partby weight of BHT and 4.16 parts by weight of MEK. Then 2.08 parts byweight of HEMA were added. The solution was heated at 50° C. for 2hours.

A solution of 1.2 parts by weight of ASATBA in 2.4 parts by weight ofMEK were added to the flask. The solution was stirred for 10 minutes,then 0.1 parts by weight of DBU and 1.0 parts by weight of deionizedwater were added. The reaction solution was heated at 50° C. for 22hours. The completeness of the reaction was confirmed by IR analysis.

EXAMPLE 22

This example describes the synthesis of a reactive blue polymeric dye:##STR33##

Into a vessel 1.64 parts by weight of azlactone monomer, 0.41 parts byweight of 1-(1-methylpropylamino)-4-(4-styrylamino)-anthraquinone (ablue dye prepared in Example 11), 0.04 parts by weight of VAZO-64 and10.0 parts by weight of MEK were charged. The solution was purged withnitrogen for 5 minutes. The vessel was sealed and placed in a constanttemperature water bath at 60° C. for 17 hours. A percent solid analysisindicated a quantitative conversion to afford a blue copolymer.

To 10.0 parts by weight of the above polymer solution were added 0.029parts by weight of DBU, 0.005 parts by weight of BHT, 1.02 parts byweight of MEK and 0.51 parts by weight of HEMA. The solution was stirredfor 30 minutes and then heated at 50° C. for 30 minutes with stirring.An IR spectrum indicated a complete reaction with HEMA.

The reaction mixture was cooled to room temperature and ASATBA (0.366parts by weight) dissolved in 0.73 parts by weight of MEK was added tothe vessel and stirred for 30 minutes. Then 0.037 parts by weight of DBUand 0.35 parts by weight of deionized water were added to the flask. Thesolution was heated at 50° C. for 10 hours. An IR spectrum analysisrevealed quantitative reaction to afford a reactive blue copolymericdye.

COMPARATIVE EXAMPLE 23

This example describes the synthesis of a reactive polymer without achromophoric moiety.

Into a reactor fitted with a condenser, a mechanical stirrer and athermometer was charged 132.0 parts by weight of azlactone monomer,264.0 parts by weight of MEK and 2.64 parts by weight of VAZO-64. Thesolution was purged for 10 minutes with nitrogen and kept under anitrogen blanket throughout the reaction. The solution was heated at 60°C. with agitation for 3.5 hours. The reaction was monitored by a percentsolid analysis and revealed quantitative conversion. The temperature ofthe solution was raised to 80° C. and maintained at this temperature for2 hours then allowed to cool to room temperature.

The solution was purged with a 90/10 nitrogen/oxygen mixture throughoutthe reaction. After 10 minutes 3.64 parts by weight of DBU were added tothe solution and agitated. A premix of 61.8 parts by weight of HEMA,0.79 parts by weight of BHT and 123.6 parts by weight of MEK were addedto the solution at such a rate to maintain the temperature below 40° C.(the reaction is exothermic). After the addition of the premix solution,the reaction mixture was stirred for 1 hour. The solution was thenheated at 50° C. for 1 hour. An IR spectrum and GC analysis indicated aquantitative reaction with HEMA.

The solution was cooled to 35° C. and a premix of 35.5 parts by weightof ASATBA with 71.3 parts by weight of MEK were added. The solution wasstirred for 30 minutes and the temperature elevated to 50° C. and heldat this temperature for 1 hour. The reaction was monitored by IR andafter 1 hour, revealed a quantitative reaction with ASATBA.

The solution was cooled to room temperature and 2.90 parts by weight ofDBU, 0.29 parts by weight of BHT and 13.4 parts by weight of deionizedwater were added. The stirred solution was heated at 50° C. for 3 hoursand 13.4 parts by weight of deionized water were added to the solutionwith continued heating at 50° C. for 8 hours. The solution was cooled toroom temperature and an IR spectrum analysis indicated a quantitativereaction with water to afford a reactive polymer. There were nodetectable azlactone rings remaining.

EXAMPLE 24

This example describes the synthesis of aspartic acid tetrabutylammoniumsalt (ASATBA).

Into a vessel 50.0 parts by weight of aspartic acid and 68.0 parts byweight of deionized water were charged. To this solution 255.87 parts byweight of tetrabutylammonium hydroxide (40% solution in water) wereadded slowly with agitation. The solution gave a clear solution aftermixing. The water was evaporated off under vacuum at 40° C. to yield aviscous clear liquid that was soluble in MEK.

COMPARATIVE EXAMPLE 25

A coating solution formulation utilizing the reactive azlactone polymeras prepared in Comparative Example 23 along with a monomeric metal-azomagenta dye as prepared in Example 4 for an overlay proofingconstruction is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.817    0.909      43.2                                       (50%)                                                                         reactive polymer (33%)                                                                       2.348    0.775      36.8                                       (Example 23)                                                                  MEK            5.430    --         --                                         wetting agent  0.062    0.062       3.0                                       monomeric colorant                                                                           0.240    0.240      11.4                                       photoinitiator 0.119    0.119       5.7                                       Total          10.01    2.105      100.1                                      ______________________________________                                    

The multifunctional oligomer, a hexafunctional acrylate was derived fromTDI (toluene diisocyanate) and prepared as described in U.S. Pat. No.4,316,949 and such description is incorporated herein by reference. MEKis a nonchlorinated hydrocarbon solvent. The wetting agent (commerciallyavailable from 3M Co. under the trade name "Fluorinert FC 430") isincluded to improve wetting of the formulation during the coating step.The colorant was a chromium based polymerizable metal-azo dye (asprepared in Example 4). The photoinitiator used was2,4-bis(trichloromethyl)-6-(3'-(2'-hydroxyethoxy)styryl)-s-triazine.

The colorant formulation was coated onto 2 mil PET (commerciallyavailable from ICI Americas under the trade designation "505") using a#15 wire-wrapped Meyer bar, dried in a convection oven at 200° F. for 2minutes and gave a dry coating weight of approximately 1.3 g/m². Thecoated construction was then exposed imagewise through a set of fourPlate Control Wedge targets (Ugra, St. Gall, Switzerland, "UGRA target")to actinic radiation using a Berkey-Ascor 5 kW vacuum frame exposureunit such that each target was exposed for 50, 60 70 and 80 units,respectively, at high intensity in increments of 10 units. An exposureof 40 units corresponded to 15 seconds. The imagewise exposedconstruction was developed using an aqueous developer solution comprisedof 1% KHCO₃, 1% Na₂ CO₃, 0.1% SURFYNOL 465 (pH of 10.2).

The image of the developed construction was evaluated by eye using a tenpower eyepiece on a light table. The best image resulted from 60 units,(22 seconds), which gave a solid four on a √2 graduated greyscale. The2% and 98% hard dots and screens where held as were the positive andnegative six microlines. The reflective optical density afterdevelopment was 1.25, the transparency 2.88, the ΔE (in the developedregions) was 9.67. The background toning as represented by ΔE was highdue to the monomeric nature of the colorant.

EXAMPLE 26

The same colorant formulation was used for a single sheet construction.It was coated onto a PET with a release layer (commercially availablefrom ICI, Americas) using a #15 Meyer bar and was dried in a convectionoven for two minutes at 200° F. This layered construction was thencoated with an acrylic thermal adhesive (commercially available fromReichold Chemical under the trade designation "97603") using a #6 Meyerbar, dried for 2 minutes at 200° F. in a convection oven, and gave a drycoating weight of approximately 1.5 g/m². This layered construction wasthen laminated to a commercially available paper base (coated on bothsides with polypropylene) using a hot roll lamination processoroperating at 280° F. for the upper roll and 180° F. for the lower rolland a transport speed of 4.

The polyester carder sheet was removed and the layered construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of four UGRA targets with 50 to 80 units athigh intensity in increments of 10 units. The imagewise exposedconstruction was developed using the aqueous developer solutiondescribed in Comparative Example 25. The 60 unit exposure gave the bestimage as determined by eye using a 10× eye piece. The image displayed 2%and 98% dots and screens and complete 8 positive and negativemicrolines. The background ΔE for this construction was 18.72. Due tothe ability of the monomeric colorant to migrate into the adhesivelayer, the ΔE was unacceptably high.

EXAMPLE 27

A metal-azo magenta dye as prepared in Example 4 was copolymerized withalkenylazlactone monomers to give an azlactone/colorant copolymer, whichwas then functionalized to give 25% HEMA, 5% aspartate, and 68%carboxylate. There was 2 mole % of the polymerizable metal-azo magentain the copolymer. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.821    0.911      47.8                                       (50%)                                                                         reactive polymer (33%)                                                                       2.445    0.807      42.3                                       Example (21)                                                                  MEK            9.834    --         --                                         wetting agent  0.075    0.075       3.9                                       photoinitiator 0.115    0.115       6.0                                       Total          14.290   1.908      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto polyester (commercially available from ICI, under the tradedesignation of 505) using a #26 Meyer bar, dried in a convection oven at200° F. for 2 minutes and gave a coating weight of approximately 1.3g/m². This colored construction was exposed to actinic radiation using aBerkey-Ascor 5 kW vacuum frame exposure unit through a set of five UGRAtargets with 30-70 units at high intensity in increments of 10 units.The imagewise exposed construction was developed using the aqueousdeveloper solution described in Comparative Example 25. The 60 unitexposure gave the best image as determined by eye using a 10× eye piece.The image displayed 2% and 98% dots and screens and complete 6 positiveand negative microlines. This had a reflective optical density: 1.34,transparency=2.82, and a background ΔE=0.83. The background toning wasdramatically decreased since the colorant was attached to the polymer.

EXAMPLE 28

A reactive magenta copolymer dye containing coating solution formulationas prepared in Example 27, for a single sheet color proofing applicationis given below:

    ______________________________________                                        Component      Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     0.826    0.413      43.2                                       (50%)                                                                         reactive polymer (33%)                                                                       1.468    0.484      50.6                                       Example (21)                                                                  MEK            2.947    --         --                                         wetting agent  0.026    0.026       2.7                                       photoinitiator 0.034    0.034       3.6                                       Total          5.301    0.957      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto a release layer coated polyester using a #26 Meyer bar,dried in a convection oven at 200° F. for 2 minutes, and gave a coatingweight of approximately 1.8 g/m². A barrier solution prepared using 5%of the functionalized reactive polymer prepared in Example 23, 3% of themultifunctional oligomer, and 1%2,4-bis(trichloromethyl)-6-(3'-(2'-hydroxyethoxy)styryl)-s-triazine inMEK was coated onto the color layer using a #6 Meyer bar, dried for 2minutes in a convection oven at 200° F. and gave a coating weight ofapproximately 0.5 g/m². This layered construction was then coated withan acrylic thermal adhesive (commercially available from ReicholdChemical under the trade designation "97603") using a #6 Meyer bar,dried for 2 minutes at 200° F. in a convection oven, and gave a drycoating weight of approximately 1.5 g/m². This layered construction wasthen laminated to a commercially available paper base (coated on bothsides with polypropylene) using a hot roll lamination processoroperating at 280° F. for the upper roll and 180° F. for the lower rolland a transport speed of 4.

The polyester support film was removed and the construction exposed toactinic radiation using a Berkey-Ascor 5 kW vacuum frame exposure unitthrough a set of five UGRA targets with 20-100 units at high intensityin increments of 20 units. The imagewise exposed construction wasdeveloped using the aqueous developer solution described in ComparativeExample 25. The 60 unit exposure gave the best image as determined byeye using a 10× eye piece. The image displayed 2% and 98% dots andscreens and complete 8 positive and negative microlines. The reflectiveoptical density=1.46, background ΔE=0.90.

EXAMPLE 29

A polymerizable metal-azo methine yellow was copolymerized withalkenylazlactone monomers to give a reactive copolymeric dye, which wasthen functionalized to give 30% HEMA, 6% aspartate, and 61% carboxylate.There was 3 mole % of the polymerizable metal-azo methine yellow in thecopolymer. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.912    0.956      24.6                                       (50%)                                                                         reactive polymer (33%)                                                                       8.262    2.727      70.2                                       Example 20                                                                    MEK            10.337   --         --                                         wetting agent  0.080    0.080       2.1                                       photoinitiator 0.122    0.122       3.1                                       Total          20.713   3.885      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto 2 mil polyester (commercially available from ICI Americas,under the trade designation "505") using a #18 Meyer bar, and dried in aconvection oven at 200° F. for 2 minutes. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of five UGRA targets with 30-70 units athigh intensity in increments of 10 units.

The imagewise exposed construction was developed using the aqueousdeveloper solution described in Comparative Example 25. The 60 unitexposure gave the best image as determined by eye using a 10× eye piece.The image displayed 2% and 98% dots and screens and complete 8 positiveand negative microlines. The reflective optical density=0.95,transparency=2.80, background ΔE=0.41.

EXAMPLE 30

A nucleophilic anthraquinone magenta dye was introduced into polymerizedazlactone to give 4% by weight of a sidechain colorant. The rest of theazlactone tings were functionalized to give 32% HEMA, 7% aspartate, and57% carboxylate. There was 4 mole % of the nucleophilic anthraquinonemagenta dye in the copolymer. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     0.751    0.376      37.3                                       (50%)                                                                         reactive polymer (16.6%)                                                                     3.013    0.500      49.6                                       Example 19                                                                    MEK            2.647    --         --                                         wetting agent  0.056    0.056       5.6                                       photoinitiator 0.077    0.077       7.6                                       Total          6.544    1.009      100.1                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This was coated ontopolyester (commercially available from ICI Americas, under the tradedesignation "505") using a #6 Meyer bar and dried in a convection overat 200° F. for 2 minutes. The colored construction was exposed toactinic radiation using a Berkey-Ascor 5 kW vacuum frame exposure unitthrough an UGRA target with 10-100 units at high intensity in incrementsof 10 units.

The imagewise exposed construction was developed using the aqueousdeveloper solution described in Comparative Example 25. The 50 unitexposure gave the best image as determined by eye using a 10× eye piece.The image displayed 2% and 98% dots and screens and complete 8 positiveand negative microlines. The reflective optical density=0.82,transparency=2.48, background ΔE=0.91.

EXAMPLE 31

A polymerizable anthraquinone yellow dye was copolymerized withazlactone monomers to give a reactive copolymeric dye, which was thenfunctionalized to give 50% HEMA, 10% aspartate, and 35% carboxylate.There was 5.0 mole % of the polymerizable anthraquinone yellow in thecopolymer. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.907    0.954      24.2                                       (50%)                                                                         reactive polymer (33.7%)                                                                     8.258    2.783      70.6                                       Example 15                                                                    MEK            9.834    --         --                                         wetting agent  0.088    0.088       2.2                                       photoinitiator 0.117    0.117       3.0                                       Total          20.913   3.942      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto polyester (commercially available from ICI Americas, underthe trade designation "505") using a #34 Meyer bar and dried in aconvection oven at 200° F. for 2 minutes. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through an UGRA target with 20-100 units at high intensityin increments of 20 units.

The imagewise exposed construction was developed using the aqueousdeveloper solution described in Comparative Example 25. The 80 unitexposure gave the best image as determined by eye using a 10× eye piece.The image displayed 2% and 98% dots and screens and complete 8 positiveand negative microlines. The reflective optical density=0.89,transparency=2.44, background ΔE=0.16.

EXAMPLE 32

A nucleophilic metal-azo magenta dye was introduced into polymerizedazlactone to give 6 mole % of a sidechain colorant. The remainingazlactone rings were functionalized to give 12% HEMA, 3% aspartate, and79% carboxylate. There was 6 mole % of the nucleophilic metal-azomagenta dye in the copolymer. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     0.939    0.470      31.7                                       (50%)                                                                         reactive polymer (7.3%)                                                                      12.226   0.892      60.3                                       Example 18                                                                    MEK            5.359    --         --                                         wetting agent  0.041    0.041       2.8                                       photoinitiator 0.077    0.077       5.2                                       Total          18.642   1.480      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto polyester (commercially available from ICI Americas, underthe trade designation "505") using a #14 Meyer bar, and dried in aconvection oven at 200° F. for 2 minutes. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of five UGRA targets with 30-150 units athigh intensity in increments of 50 units.

The imagewise exposed construction was developed using the aqueousdeveloper solution described in Comparative Example 25. The 60 unitexposure gave the best image as determined by eye using a 10× eye piece.The image displayed 2% and 98% dots and screens and complete 8 positiveand negative microlines. The reflective optical density=1.49,transparency=2.15, background ΔE=1.30.

EXAMPLE 33

A polymerizable yellow anthraquinone dye was copolymerized withazlactone (as prepared in Example 15). The remaining azlactone ringswere functionalized to give 50% HEMA, 10% aspartate, 35% carboxylate and5% yellow dye. The formulation is given below:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.406    0.703      47.7                                       (50%)                                                                         reactive polymer (7.3%)                                                                      6.181    0.451      30.6                                       Example 15                                                                    MEK            4.215    --         --                                         wetting agent (43.8%)                                                                        0.404    0.177      12.0                                       photoinitiator 0.143    0.143       9.7                                       Total          12.349   1.474      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto 2 mil PET (commercially available from ICI Americas, underthe trade designation "505") using a #10 Meyer bar, and dried in aconvection oven at 200° F. for one minute. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of five UGRA targets with 2-10 units at lowintensity in increments of 2 units. A piece of commercially availablepaper base was coated with an acrylic adhesive. The exposed constructionwas laminated with the adhesive-coated paper base using a hot rolllamination processor operating at 280° F. for the upper roll and 180° F.for the lower roll and a transport speed of 4. The laminatedconstruction was cooled to room temperature and the PET was peeled offto afford a positive image on the paper base and a negative image on thePET. The 6 unit exposure gave the best image as determined by eye usinga 10× eye piece. The image displayed 5% and 95% dots and screens andcomplete 10 positive and negative microlines.

EXAMPLE 34

A polymerizable metal-azo magenta dye was copolymerized with azlactone(as prepared in Example 21) and was functionalized to give 25% HEMA, 5%aspartate, 68% carboxylate and 2% magenta dye. The formulation is givenbelow:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.383    0.692      27.6                                       (50%)                                                                         reactive polymer (15%)                                                                       9.697    1.455      57.9                                       Example 21                                                                    wetting agent (43.8%)                                                                        0.513    0.225       9.0                                       photoinitiator 0.140    0.140       5.6                                       Total          11.733   2.512      100.1                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto 2 mil PET (commercially available from ICI Americas, underthe trade designation "505") using a #10 Meyer bar, and dried in aconvection oven at 200° F. for 2 minutes. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of five UGRA targets with 2-10 units at lowintensity in increments of 2 units. This exposed film was laminated toan adhesive coated paper base as described in Example 33. The laminatedconstruction was peeled off the paper base to afford a positive image onthe paper base and a negative image on the PET. The 10 unit exposuregave the best image on the paper base as determined by eye using a 10×eye piece. The image displayed 2% and 98% dots and screens and 6positive and negative microlines.

EXAMPLE 35

A polymerizable cyan anthraquinone dye was copolymerized with azlactone(as prepared in Example 22) and was functionalized to give 33% HEMA, 8%aspartate, 51% carboxylate and 8% cyan dye. The formulation is givenbelow:

    ______________________________________                                        Component                                                                     (% Solids)     Wt (g)   Wt solids (g)                                                                            % Solids                                   ______________________________________                                        multifunctional oligomer                                                                     1.398    0.699      35.1                                       (50%)                                                                         reactive polymer (16.6%)                                                                     5.319    0.883      44.3                                       Example 22                                                                    wetting agent (43.9%)                                                                        0.513    0.225      11.3                                       photoinitiator 0.186    0.186       9.3                                       Total          7.416    1.993      100.0                                      ______________________________________                                    

The wetting agent, photoinitiator and multifunctional oligomer used werethose described in Comparative Example 25. This colorant formulation wascoated onto 2 mil PET (commercially available from ICI Americas, underthe trade designation "505") using a #10 Meyer bar, and dried in aconvection oven at 200° F. for 2 minutes. The colored construction wasexposed to actinic radiation using a Berkey-Ascor 5 kW vacuum frameexposure unit through a set of five UGRA targets with 2-10 units at lowintensity in increments of 2 units. This exposed film was laminated toan adhesive coated paper base as described in Example 33. The laminatedconstruction was peeled off the paper base to afford a positive image onthe paper base and a negative image on the PET. The 10 unit exposuregave the best image on the paper base as determined by eye using a 10×eye piece. The image displayed 2% and 98% dots and screens and 6positive and negative microlines.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodimentsset forth herein above.

We claim:
 1. A colorant layer formulation comprising(a) a reactivepolymeric dye, wherein the reactive polymeric dye comprises: repeatingunits of azlactone wherein 0.1 to 99.9% by mole of the azlactonerepeating units are functionalized with a nucleophilic dye selected fromthe group consisting of metal-azo, metal-ago methine, anthraquinone,hydrazone, indoaniline, and aminostyryl dyes and the remaining azlactonerepeating units are functionalized with one or more nucleophilic groups,such that one or more of the nucleophilic groups contain afree-radically polymerizable group, an aqueous solubilizing group orcombination thereof, (b) a photoinitiator, (c) a multi functionalacrylate, (d) a surfactant, (e) a sensitizing dye,or a mixture ofcomponents (b) through (e).
 2. The colorant layer formulation accordingto claim 1, wherein the reactive polymeric dye comprises repeating unitsof azlactone and a free-radically polymerizable dye.
 3. The colorantlayer formulation according to claim 2, wherein the free-radicallypolymerizable dye has a chromophoric moiety selected from the groupconsisting of anthraquinone, metal-azo methine, metal-azo, azo,indoaniline, aminostyryl and hydrazone moiety.
 4. The colorant layerformulation according to claim 2, wherein the azlactone repeating unitsare functionalized with one or more nucleophilic groups.
 5. The colorantlayer formulation according to claim 4, wherein one of the nucleophilicgroups contains a free-radically polymerizable group.
 6. The colorantlayer formulation according to claim 4, wherein one of the nucleophilicgroups contains an aqueous solubilizing group.
 7. The colorant layerformulation according to claim 4, wherein the azlactone repeating unitsare functionalized with nucleophilic groups containing a free-radicallypolymerizable group and nucleophilic groups containing an aqueoussolubilizing group.